Methods of producing polyanthracene and uses thereof

ABSTRACT

The present application provides methods of producing polyanthracene including polymerization of anthracene monomers in the presence of oxidants and reaction solvents. The present application further provides polyanthracene produced by methods described herein that has higher solubility in organic solvents and better thermal stability and ablation resistance.

RELATED APPLICATIONS

The instant application is the U.S. National Phase under 35 U.S.C. §371of International Application No. PCT/CN2010/073532 entitled METHODS OFPRODUCING POLYANTHRACENE AND USES THEREOF, filed Jun. 4, 2010,designating the U.S. The content of this application is hereinincorporated by reference in its entirety.

BACKGROUND

Polyanthracene is a π-conjugated polymer of anthracene monomers. It hasattracted lots of attention in fundamental physics studies and potentialapplications in optoelectronics and microelectronics. Polyanthracene isusually prepared through two methods: electrochemical synthesis andchemical polymerization. However, the two methods have shortcomings inpractical application. For example, the electrochemical synthesis methodrequires complicated reaction equipment, and the polyanthracene yield islow due to size limitations of the electrode area. The chemicalpolymerization method involves dangerous and potentially violentreactions and the production yield is also low.

Furthermore, the polyanthracene obtained from the two methods mentionedabove have some limitations in physical characteristics. First, thepolyanthracene has low solubility in common organic solvents such astetrahydrofuran and chloroform. Second, the polyanthracene typically hasa low degree of polymerization, and thus shows low thermal stability andlow char yield.

In one study using an electrochemical method, anthracene was polymerizedusing boron trifluoride diethyl etherate as an electrolyte. According tothe study, polyanthracene with 4-17 repeating anthracene units wasobtained, its conductivity was measured as around 0.1 S/cm, and theproduct yield was calculated to be approximately 25% (B. Fan, et al,“Electrochemical polymerization of anthracene in boron trifluoridediethyl etherate”, Journal of Electroanalytical Chemistry, 575:287-292(2005)).

SUMMARY

In one aspect, the present disclosure provides a method of producingpolyanthracene including polymerizing anthracene monomers in thepresence of an oxidant and a reaction solvent.

In another aspect, the present disclosure provides a method of producingpolyanthracene including polymerizing anthracene monomers in thepresence of an oxidant, a reaction solvent and water.

In another aspect, the present disclosure provides a polyanthraceneproduced by a method including polymerizing anthracene monomers in thepresence of an oxidant and a reaction solvent.

In another aspect, the present disclosure provides a polyanthracenecontaining 18 or more units of anthracene monomers.

In another aspect, the present disclosure provides a polyanthracenewhich is soluble in organic solvent.

In another aspect, the present disclosure provides a polyanthraceneuseful for making thermal stable materials or ablation resistantmaterials.

In another aspect, the present disclosure provides a compositionincluding a polyanthracene produced by a method described herein.

In another aspect, the present disclosure provides a compositionincluding a polyanthracene in which 5% to 80% of the polyanthracene byweight contains 18 or more units of anthracene monomers

The foregoing summary is illustrative only and is not intended to be inany way limiting. In addition to the illustrative aspects, embodiments,and features described above, further aspects, embodiments, and featureswill become apparent by reference to the drawings and the followingdetailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an illustrative polymerization reaction for producingpolyanthracene.

FIG. 2 shows the measurement results indicating the number of monomerunits and the molecular weight of polyanthracene produced by the methoddescribed in Example 1 of this application.

FIG. 3 shows absorption peaks at the wavelengths of 380 nm, 470 nm, 480nm, 610 nm and 690 nm of polyanthracene produced by the method describedin Example 2 of this application.

FIG. 4 shows absorption peaks at the wavelengths of 380 nm, 460 nm, and480 nm of polyanthracene produced by the method described in Examples3-6 of this application.

FIG. 5 shows TG (Thermogravimetric Analysis), DTG (DifferentialThermogravimetric Analysis) and DTA (Differential Thermal Analysis) ofpolyanthracene produced by the method described in Examples 4 and 6 ofthis application. Thermal analysis is conducted in nitrogen atmosphere,at a scanning rate of 20° C./min (a, b) or 10° C./min (c).

DETAILED DESCRIPTION

In the following detailed description, reference is made to theaccompanying drawings, which form a part hereof. The illustrativeembodiments described in the detailed description, drawings, and claimsare not meant to be limiting. Other embodiments may be utilized, andother changes may be made, without departing from the spirit or scope ofthe subject matter presented here.

In one aspect, the present disclosure provides a method of producingpolyanthracene, including polymerizing anthracene monomers in thepresence of an oxidant and a reaction solvent.

The term “oxidant” refers to one or more substances that can gainelectrons in a reduction-oxidation reaction. In an illustrativeembodiment, the oxidant is a Lewis acid or a combination of more thanone Lewis acid. In another illustrative embodiment, the oxidantincludes, but is not limited to one or more of: FeCl₃, FeBr₃, AlCl₃,AlBr₃, AlI₃, AlRCl₂, AlR₂Cl, AlR₃, CuCl₂, CuBr₂, MoCl₅, SnCl₄, SnBr₄,SnI₄, MgCl₂, MgBr₂, MgI₂, CaCl₂, CaBr₂, CaI₂, ZnCl₂, ZnBr₂, ZnI₂, BF₃,TiCl₄, TiBr₄, SbCl₅, and any combination thereof. In anotherillustrative embodiment, the oxidant is FeCl₃.

The term “reaction solvent” is an organic solvent that may be used inthe reaction to promote and facilitate the oxidation reaction. Thereaction solvent may contain one or more organic chemical compounds inliquid form under the reaction temperature, such as but not limited to,nitroalkanes, aromatic nitro compounds, hydrocarbons, halogenatedhydrocarbons, nitriles and any combination thereof. Hydrocarbons areorganic compounds consisting of entirely hydrogen and carbon.Illustrative examples include, but are not limited to, hexane, benzene,and isooctane. Nitroalkanes are saturated hydrocarbon derivatives havingat least one nitro group (—NO₂). Illustrative examples include, but arenot limited to, nitromethane, nitroethane, 1-nitropropane, and2-nitropropane. Aromatic nitro compounds are organic compounds having atleast one benzene ring and at least one nitro group attached to thebenzene ring. Illustrative examples include, but are not limited to,nitrobenzene, and dinitrobenzene. Halogenated hydrocarbons arehydrocarbon derivatives having at least one halogen. Illustrativeexamples include, but are not limited to, dichlorobenzene, bromoethane,chloroform, CH₃—CHCl₂, CH₃—CHCl₂, CH₂Cl—CH₂Cl, CH₂Cl₂, and bromopentane.Nitriles are organic compounds having at least one —C≡N functionalgroup. Illustrative examples include, but are not limited to,acetonitrile, propionitrile and butyronitrile. In another illustrativeembodiment, the reaction solvent includes, but is not limited to one ormore of: nitromethane(CH₃NO₂), nitroethane(CH₃CH₂NO₂), nitrobenzene,dinitrobenzene, hexane, benenze, pentane, isooctane, cyclohexane,dichloromethane, chloroform, dichloroethane, dichlorobenzene,bromoethane, dibromoethane, bromobenzene, dibromobenzene, bromopentane,carbon tetrachloride, acetonitrile, propionitrile, butyronitrile, andany combination thereof.

The reaction solvent should be able to at least partially (orcompletely) dissolve anthracene and/or the oxidant. In certainembodiments, the reaction solvent can at least partially (or completely)dissolve the anthracene monomer. In an illustrative embodiment, theanthracene monomer dissolved in the reaction solvent is at least 5%, atleast 10%, at least 20%, at least 30%, at least 40%, at least 50%, atleast 60%, at least 70%, at least 80%, or at least 90% of the totalweight of the anthracene monomer present in the reaction solvent. In anillustrative embodiment, the anthracene monomer dissolved in thereaction solvent is between 5%-100%, between 5%-90%, between 5%-80%,between 5%-70%, between 5%-60%, between 5%-50%, between 5%-40%, between5%-30%, between 5%-20%, between 5%-10%, between 10%-100%, between10%-90%, between 10%-80%, between 10%-70%, between 10%-60%, between10%-50%, between 10%-40%, between 10%-30%, or between 10%-20% of thetotal weight of the anthracene monomer present in the reaction solvent.

In certain embodiments, the reaction solvent can at least partially (orcompletely) dissolve the oxidant. In an illustrative embodiment, theoxidant dissolved in the reaction solvent is at least 5%, at least 10%,at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, atleast 70%, at least 80%, or at least 90% of the total weight of theoxidant present in the reaction solvent. In an illustrative embodiment,the oxidant dissolved in the reaction solvent is between 5%-100%,between 5%-90%, between 5%-80%, between 5%-70%, between 5%-60%, between5%-50%, between 5%-40%, between 5%-30%, between 5%-20%, between 5%-10%,between 10%-100%, between 10%-90%, between 10%-80%, between 10%-70%,between 10%-60%, between 10%-50%, between 10%-40%, between 10%-30%, orbetween 10%-20% of the total weight of the oxidant present in thereaction solvent.

In certain embodiments, the reaction solvent consists of one organicsolvent that at least partially (or completely) dissolves both theanthracene monomer and the oxidant. Illustrative examples of suchreaction solvents include, but are not limited to nitroalkanes such asbut not limited to nitromethane and nitroethane, hydrocarbons,halogenated hydrocarbons, and nitriles. In certain embodiments, thereaction solvent contains a mixture of different organic solvents thatcan at least partially (or completely) dissolve both the anthracenemonomer and the oxidant. Illustrative examples of such reaction solventsinclude but are not limited to, halogenated hydrocarbon/nitroalkane suchas dichloromethane/nitromethane, dichloroethane/nitromethane,dichloromethane/nitroethane, dichloroethane/nitroethane; halogenatedhydrocarbon/aromatic nitro compound such asdichloromethane/nitrobenzene, and dichloroethane/nitrobenzene;hydrocarbon/nitroalkane such as benzene/nitromethane, andbenzene/nitroethane; hydrocarbon/aromatic nitro compound such asn-hexane/nitrobenzene, and benzene/nitrobenzene; andnitriles/nitroalkane such as acetonitrile/nitromethane.

In certain embodiments, the reaction solvent may contain a first organicsolvent that can at least partially (or completely) dissolve theanthracene monomer, and a second organic solvent that can at leastpartially (or completely) dissolve the oxidant, and the two solvents aremutually miscible. Illustrative examples include but are not limited to,dichloromethane/nitromethane, dichloroethane/nitromethane, andbenzene/nitromethane. In certain embodiments, the reaction solvent maycontain a first organic solvent that can at least partially (orcompletely) dissolve the anthracene monomer, and a second organicsolvent that can at least partially (or completely) dissolve theoxidant, and the two reaction solvents cannot dissolve into each otherand thus would separate into two phases when mixed together.Illustrative examples include but are not limited to,n-hexane/nitromethane, cyclohexane/nitromethane, i-pentane/nitromethane,n-pentane/nitromethane, and isooctane/nitromethane, etc. Furthermore,the first organic solvent and the second organic solvent may eachconsist of one or more organic compounds.

In an illustrative embodiment, the present disclosure provides a methodof producing polyanthracene, including polymerizing anthracene monomersin the presence of an oxidant and a reaction solvent, in which the molarratio of the oxidant to the anthracene monomers is in the range from 1:1to 9:1. In another illustrative embodiment, the molar ratio of theoxidant to the anthracene monomers is in the range from 1:1 to 8:1. Inanother illustrative embodiment, the molar ratio of the oxidant to theanthracene monomers is in the range from 1:1 to 7:1. In anotherillustrative embodiment, the molar ratio of the oxidant to theanthracene monomers is in the range from 1:1 to 6:1. In anotherillustrative embodiment, the molar ratio of the oxidant to theanthracene monomers is in the range from 1:1 to 5:1. In anotherillustrative embodiment, the molar ratio of the oxidant to theanthracene monomers is in the range from 1:1 to 4:1. In anotherillustrative embodiment, the molar ratio of the oxidant to theanthracene monomers is in the range from 1:1 to 3:1. In anotherillustrative embodiment, the molar ratio of the oxidant to theanthracene monomers is in the range from 1:1 to 2:1.

In an illustrative embodiment, the present disclosure provides a methodof producing polyanthracene, including polymerizing anthracene monomersin the presence of an oxidant and a reaction solvent, in which thepolymerization is conducted at the reaction temperature ranging from 20°C. to 100° C. In another illustrative embodiment, the reactiontemperature is from 20° C. to 80° C. In another illustrative embodiment,the reaction temperature is from 20° C. to 60° C. In anotherillustrative embodiment, the reaction temperature is from 20° C. to 50°C. In another illustrative embodiment, the reaction temperature is from20° C. to 45° C. In another illustrative embodiment, the reactiontemperature is from 20° C. to 40° C. In another illustrative embodiment,the reaction temperature is from 20° C. to 35° C. In anotherillustrative embodiment, the reaction temperature is from 20° C. to 30°C. In another illustrative embodiment, the reaction temperature is at orabove about 20° C., 21° C., 22° C., 23° C., 24° C., or 25° C., but nothigher than about 100° C. The reaction temperature can be monitoredand/or measured using a thermometer appropriately submerged in thereaction mixture or in the bath surrounding the reaction mixture.

In an illustrative embodiment, the present disclosure provides a methodof producing polyanthracene, including polymerizing anthracene monomersin the presence of an oxidant and a reaction solvent, in which thepolymerization is conducted for a reaction time of 1 to 24 hours. Inanother illustrative embodiment, the reaction time is 2 to 12 hours. Inanother illustrative embodiment, the reaction time is 6 to 8 hours. Inanother illustrative embodiment, the reaction time is for up to 4 hours,6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20hours, 22 hours or 24 hours. In another illustrative embodiment, thereaction time is at least 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours.

In an illustrative embodiment, the present disclosure provides a methodof producing polyanthracene, including polymerizing anthracene monomersin the presence of an oxidant, a reaction solvent, and water. In anotherillustrative embodiment, the water constitutes at least 1%, 5%, 10%,20%, 30%, 40%, or 50% in volume of the polymerization reaction mixture.In another illustrative embodiment, the water constitutes about 1% to5%, about 5% to 10%, about 10% to 15%, about 15% to 20%, about 20% to25%, about 25% to 30%, about 30% to 35%, about 35% to 40%, about 40% to45%, or about 45% to 50% in volume of the polymerization reactionmixture. In another illustrative embodiment, the water constitutes about1% to 10%, about 5% to 20%, about 10% to 30%, about 20% to 40%, about30% to 50%, about 40% to 50%, about 1% to 50%, about 5% to 40%, about10% to 40%, or about 20% to 30% in volume of the polymerization reactionmixture.

In another aspect, the present disclosure provides a polyanthraceneproduced by a method described herein. In an illustrative embodiment,the oxidant is a Lewis acid or a combination of more than one Lewisacid. In another illustrative embodiment, the oxidant includes, but isnot limited to one or more of FeCl₃, FeBr₃, AlCl₃, AlBr₃, AlI₃, AlRCl₂,AlR₂Cl, AlR₃, CuCl₂, CuBr₂, MoCl₅, SnCl₄, SnBr₄, SnI₄, MgCl₂, MgBr₂,MgI₂, CaCl₂, CaBr₂, CaI₂, ZnCl₂, ZnBr₂, ZnI₂, BF₃, TiCl₄, TiBr₄, SbCl₅,and any combination thereof. In another illustrative embodiment, theoxidant is FeCl₃. In another illustrative embodiment, the reactionsolvent is nitroalkanes, aromatic nitro compounds, hydrocarbons,halogenated hydrocarbons, and/or nitriles. In another illustrativeembodiment, the reaction solvent includes, but is not limited to one ormore of: nitromethane, nitroethane, nitrobenzene, dinitrobenzene,hexane, benenze, pentane, isooctane, cyclohexane, dichloromethane,chloroform, dichloroethane, dichlorobenzene, bromoethane, dibromoethane,bromobenzene, dibromobenzene, bromopentane, carbon tetrachloride,acetonitrile, propionitrile, butyronitrile, and any combination thereof.

In an illustrative embodiment, the present disclosure provides apolyanthracene produced by a method including polymerizing anthracenemonomers in the presence of an oxidant and a reaction solvent, in whichthe molar ratio of the oxidant to the anthracene monomers is in therange from 1:1 to 9:1. In another illustrative embodiment, the molarratio of the oxidant to the anthracene monomers is in the range from 1:1to 8:1. In another illustrative embodiment, the molar ratio of theoxidant to the anthracene monomers is in the range from 1:1 to 7:1. Inanother illustrative embodiment, the molar ratio of the oxidant to theanthracene monomers is in the range from 1:1 to 6:1. In anotherillustrative embodiment, the molar ratio of the oxidant to theanthracene monomers is in the range from 1:1 to 5:1. In anotherillustrative embodiment, the molar ratio of the oxidant to theanthracene monomers is in the range from 1:1 to 4:1. In anotherillustrative embodiment, the molar ratio of the oxidant to theanthracene monomers is in the range from 1:1 to 3:1. In anotherillustrative embodiment, the molar ratio of the oxidant to theanthracene monomers is in the range from 1:1 to 2:1.

In an illustrative embodiment, the present disclosure provides apolyanthracene produced by a method including polymerizing anthracenemonomers in the presence of an oxidant and a reaction solvent, in whichthe polymerization is conducted at the reaction temperature ranging from20° C. to 100° C. In another illustrative embodiment, the reactiontemperature ranges from 20° C. to 80° C. In another illustrativeembodiment, the reaction temperature ranges from 20° C. to 60° C. Inanother illustrative embodiment, the reaction temperature ranges from20° C. to 50° C. In another illustrative embodiment, the reactiontemperature ranges from 20° C. to 45° C. In another illustrativeembodiment, the reaction temperature ranges from 20° C. to 40° C. Inanother illustrative embodiment, the reaction temperature ranges from20° C. to 35° C. In another illustrative embodiment, the reactiontemperature ranges from 20° C. to 30° C. In another illustrativeembodiment, the reaction temperature is at or above about 20° C., 21°C., 22° C., 23° C., 24° C., or 25° C., but not higher than about 100° C.

In an illustrative embodiment, the present disclosure provides apolyanthracene produced by a method including polymerizing anthracenemonomers in the presence of an oxidant and a reaction solvent, in whichthe polymerization is conducted for a reaction time ranging from 1 to 24hours. In another illustrative embodiment, the reaction time ranges from2 to 12 hours. In another illustrative embodiment, the reaction timeranges from 6 to 8 hours. In another illustrative embodiment, thereaction time is for up to 4 hours, 6 hours, 8 hours, 10 hours, 12hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours. Inanother illustrative embodiment, the reaction time is at least 1 hour, 2hours, 3 hours, 4 hours, or 5 hours.

In an illustrative embodiment, the present disclosure provides apolyanthracene produced by a method including polymerizing anthracenemonomers in the presence of an oxidant, a reaction solvent, and water.In another illustrative embodiment, the polymerization reaction mixturecontains at least 1%, 5%, 10%, 20%, or 50% water by volume.

In an illustrative embodiment, the present disclosure provides apolyanthracene produced by a method described herein, in which thepolyanthracene contains 18 or more units of anthracene monomers. Inanother illustrative embodiment, the present disclosure provides apolyanthracene which contains 18 or more units of anthracene monomers.In another illustrative embodiment, the polyanthracene of the presentdisclosure contains 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31,32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49,50 or more units of anthracene monomers. In another illustrativeembodiment, the polyanthracene contains 18 to 25 units of anthracenemonomers. In another illustrative embodiment, about 5% to 80% of thepolyanthracene by weight contains 18 or more units of anthracenemonomers. In another illustrative embodiment, about 10% to 50% of thepolyanthracene by weight contains 18 or more units of anthracenemonomers. In another illustrative embodiment, about 20% to 30% of thepolyanthracene by weight contains 18 or more units of anthracenemonomers. The number of anthracene monomer units in a polyanthracene canbe determined by matrix-assisted laser desorption/ionizationtime-of-flight mass spectrometer (MALDI-TOF-MS) (W. Schrepp, H. Pasch,“Maldi-Tof Mass Spectrometry of Synthetic Polymers” (SpringerLaboratory) (2003), Berlin: Springer-Verla; Nielen, Michel W. F.,“Characterization of polydisperse synthetic polymers by size-exclusionchromatography/matrix-assisted laser desorption/ionizationtime-of-flight mass spectrometry”, Rapid Communications in MassSpectrometry 11: 1194 (1997).).

In an illustrative embodiment, the present disclosure provides acomposition including a polyanthracene, in which the polyanthracenecontains 18 or more units of anthracene monomers. In anotherillustrative embodiment, the present disclosure provides a compositionincluding a polyanthracene, in which 5% to 80% of the polyanthracene byweight contains 18 or more units of anthracene monomers.

In an illustrative embodiment, the present disclosure provides apolyanthracene produced by a method described herein, in which about 5%to 95% of the polyanthracene has a weight average molecular weight ofabout 500 to 10,000. In another illustrative embodiment, the presentdisclosure provides a polyanthracene, in which about 5% to 95% of thepolyanthracene has a weight average molecular weight of about 500 to10,000. In another illustrative embodiment, the polyanthracene of thepresent disclosure has a molecular weight of about 500 to 9000, about500 to 8,000, about 500 to 7,000, about 500 to 6,500, about 500 to6,000, about 500 to 5,000, about 500 to 4,500, about 500 to 4,000, about500 to 3,500, about 500 to 3,000, about 500 to 2,500, about 500 to2,000, about 500 to 1,500, about 500 to 1,000, about 1,000 to 10,000,about 2,000 to 10,000, about 3,000 to 10,000, about 4,000 to 10,000,about 5,000 to 10,000, about 6,000 to 10,000, about 7,000 to 10,000,about 8,000 to 10,000, or about 9,000 to 10,000. The molecular weight ofpolyanthracene can be determined by gel permeation chromatography usingpolystyrene standards (A. Kumar et al, “Fundamentals of PolymerEngineering”, published by CRC Press, Edition 2, Chapter 8 section 7, p364-368 (2003)).

In an illustrative embodiment, the present disclosure provides apolyanthracene produced by a method described herein, in which thepolyanthracene has a thermal decomposition temperature between about300° C. and 1000° C. In another illustrative embodiment, the presentdisclosure provides a polyanthracene having a thermal decompositiontemperature between about 300° C. and 1000° C. In another illustrativeembodiment, the polyanthracene of the present disclosure has a thermaldecomposition temperature between about 300° C. and 900° C., betweenabout 400° C. and 900° C., between about 500° C. and 900° C., betweenabout 600° C. and 900° C., between about 700° C. and 900° C., betweenabout 800° C. and 900° C., between about 300° C. and 800° C., betweenabout 300° C. and 700° C., between about 300° C. and 600° C., betweenabout 300° C. and 500° C., or between about 300° C. and 400° C. in thepresence of nitrogen. The term “thermal decomposition temperature”refers to the temperature at which the weight loss of polyanthracenereaches the maximum speed. The thermal decomposition temperature can bedetermined by the thermogravimetric analysis (TGA) (J. Menczel, B.Prime, “Thermal Analysis of Polymers, Fundamentals and Applications”,published by John Wiley & Sons, Inc., Hoboken, N.J., Chapter 3, p.241-311 (2009)).

In an illustrative embodiment, the present disclosure provides apolyanthracene produced by a method described herein, in which theelectrical conductivity of the polyanthracene is about 10⁻⁹ to 10⁻¹¹ Scm⁻¹. In another illustrative embodiment, the present disclosureprovides a polyanthracene having an electrical conductivity of about10⁻⁹ to 10⁻¹¹ S cm⁻¹. In another illustrative embodiment, the electricalconductivity of the polyanthracene of the present disclosure is about7×10⁻⁹ to 10⁻¹¹ S cm⁻¹. Electrical conductivity of the polyanthracenecan be measured by dissolving the polyanthracene in a solvent to preparea solution and measuring the electrical resistance of the solution usinga multimeter at room temperature.

In an illustrative embodiment, the present disclosure provides apolyanthracene produced by a method described herein, in which the charyield of the polyanthracene at 1000° C. is not lower than 70%. Inanother illustrative embodiment, the present disclosure provides apolyanthracene having a char yield at 1000° C. of not lower than 70%. Inanother illustrative embodiment, the char yield of the polyanthracene ofthe present disclosure at 1000° C. is not lower than 75%. In anotherillustrative embodiment, the char yield of the polyanthracene at 1000°C. is not lower than 80%. In another illustrative embodiment, the charyield of the polyanthracene at 1000° C. is not lower than 85%. Inanother illustrative embodiment, the char yield of the polyanthracene at1000° C. is from 70% to 95%, from 70% to 90%, from 70% to 85%, or from70% to 80%. To obtain the char, the polyanthracene is heated at a rateof 20° C. min⁻¹ in a chamber with nitrogen flow at a rate of 40 m min⁻¹.The char yield is calculated as the percentage of the weight of theremaining substance to the initial weight of the polyanthracene.

In an illustrative embodiment, the present disclosure provides apolyanthracene produced by a method described herein, in which theproduced polyanthracene is at least partially (or completely) soluble inan organic solvent. In another illustrative embodiment, the presentdisclosure provides a polyanthracene which is at least partially (orcompletely) soluble in an organic solvent. In another illustrativeembodiment, the polyanthracene of the present disclosure that can bedissolved in the organic solvent is at least 5%, at least 10%, at least20%, at least 30%, at least 40%, at least 50%, at least 60%, at least70%, at least 80%, or at least 90% of the total weight of thepolyanthracene present in the organic solvent. In another illustrativeembodiment, the polyanthracene dissolved in the organic solvent isbetween 5%-100%, between 5%-90%, between 5%-80%, between 5%-70%, between5%-60%, between 5-50%, between 5%-40%, between 5%-30%, between 5%-20%,between 5%-10%, between 10%-100%, between 10%-90%, between 10%-80%,between 10%-70%, between 10%-60%, between 10%-50%, between 10%-40%,between 10%-30%, or between 10%-20% of the total weight of thepolyanthracene present in the organic solvent. In another illustrativeembodiment, 5%-100% of the polyanthracene by weight is soluble in theorganic solvent. Illustrative examples of organic solvents in which thepolyanthracene is soluble include, but are not limited to, esters suchas ethyl acetate and n-butyl acetate, ketones such as acetone and methylethyl ketone, alcohols such as ethanol and isopropanol, ethers such asdiethyl ether and dioxane, aliphatic or aromatic hydrocarbons such astoluene and cyclohexane, and any mixture thereof. In anotherillustrative embodiment, the polyanthracene is at least partially (orcompletely) soluble in polar organic solvents, including withoutlimitation, N-methylpyrrolidone (NMP), tetrahydrofuran (THF),chloroform, dimethylformamide (DMF), and/or dimethylsulfoxide (DMSO). Inanother illustrative embodiment, 5%-100% of the polyanthracene by weightis soluble in the organic solvent including, but not limited to one ormore of: N-methylpyrrolidone (NMP), tetrahydrofuran (THF), chloroform,dimethylformamide (DMF), and dimethylsulfoxide (DMSO).

In an illustrative embodiment, the present disclosure provides apolyanthracene produced by a method described herein, in which theproduced polyanthracene has absorbance peaks at wavelengths ranging fromabout 380 nm to about 690 nm. In another illustrative embodiment, thepresent disclosure provides a polyanthracene having absorbance peaks atwavelengths ranging from about 380 nm to about 690 nm. In anotherillustrative embodiment, the polyanthracene of the present disclosurehas absorbance peaks at wavelengths ranging from about 470 nm to about690 nm. In another illustrative embodiment, the polyanthracene hasabsorbance peaks at wavelengths ranging from about 600 nm to about 690nm.

In an illustrative embodiment, the present disclosure provides acomposition including a plurality of anthracene monomers and an oxidant.In another illustrative embodiment, the oxidant includes, but is notlimited to one or more of: FeCl₃, FeBr₃, AlCl₃, AlBr₃, AlI₃, AlRCl₂,AlR₂Cl, AlR₃, CuCl₂, CuBr₂, MoCl₅, SnCl₄, SnBr₄, SnI₄, MgCl₂, MgBr₂,MgI₂, CaCl₂, CaBr₂, CaI₂, ZnCl₂, ZnBr₂, ZnI₂, BF₃, TiCl₄, TiBr₄, SbCl₅,and any combination thereof. In another illustrative embodiment, thecomposition further includes a reaction solvent. In another illustrativeembodiment, the reaction solvent is nitroalkanes, aromatic nitrocompounds, hydrocarbons, halogenated hydrocarbons, and/or nitriles. Inanother illustrative embodiment, the reaction solvent includes, but isnot limited to one or more of: nitromethane, nitroethane, nitrobenzene,dinitrobenzene, hexane, benenze, pentane, isooctane, cyclohexane,dichloromethane, chloroform, dichloroethane, dichlorobenzene,bromoethane, dibromoethane, bromobenzene, dibromobenzene, bromopentane,carbon tetrachloride, acetonitrile, propionitrile, butyronitrile, andany combination thereof. In another illustrative embodiment, thecomposition further includes water. In another illustrative embodiment,the water constitutes at least 1%, 5%, 10%, 20%, 30%, 40%, or 50% involume of the composition. In another illustrative embodiment, the waterconstitutes about 1% to 5%, about 5% to 10%, about 10% to 15%, about 15%to 20%, about 20% to 25%, about 25% to 30%, about 30% to 35%, about 35%to 40%, about 40% to 45%, or about 45% to 50% in volume of thecomposition.

The polyanthracene of the present disclosure has high thermal stabilityand ablation resistance. Ablation is an erosive phenomenon in which, asa material is exposed to high temperatures such as above 1200° C., partsof the material are eroded by thermal oxidation. Substances undergoingablation may be removed by combustion flames with high pressure andvelocity. Materials having ablation resistance can have a low erosionrate and long material lifetime even when exposed to high or extremelyhigh temperatures. The resistance to ablation of the polyanthraceneproduct may be tested by an ablation test such as without limitationoxyacetylene ablation testing. For example, in oxyacetylene ablationtesting, hot combustion gases (such as oxyacetylene) can be directedalong the direction perpendicular to the center of the specimen ofpolyanthracene until burn-through is achieved. The erosion rate of thepolyanthracene can be determined by dividing the original thickness ofthe specimen by the time required for burn-through (ASTM Standard E285-80, (2002), “Standard Test Method for Oxyacetylene Ablation Testingof Thermal Insulation Materials,” ASTM International, West Conshohocken,Pa., www.astm.org; Najim, T. et al, “Thermal and Ablative Properties ofIpns and Composites of High Ortho Resole Resin and DifurfurylideneAcetone”, Leonardo Electronic Journal of Practices and Technologies,13:34-46 (2008)). Other methods for ablation test may also be used, forexample, the polyanthracene product can be exposed to flames that areapplied to the product at certain speeds and temperatures for a certainperiod of time and observe the effects of such flame on the product.

In another aspect, the present disclosure provides a polyanthraceneuseful for making thermostable materials or ablation resistantmaterials. The thermal stable materials or ablation resistant materialsmay be made by any method known to a person skilled in the art. Inbrief, in an illustrative embodiment, the materials may be made byproducing the polyanthracene using the methods described herein,isolating and purifying the resulting polyanthracene, making thepolyanthracene into the desired shape and structure such as powder,film, foam, sheet, block, solution and paste. The ablation resistantpolyanthracene of the present disclosure may be used as protectivesurface materials for any surface, such as but not limited to,machinery, construction, buildings and steel structures etc, that mayrequire resistance to fire and extremely high heat.

Furthermore, the polyanthracene described herein can be used asprecursor materials for making a variety of carbon materials andcomposite carbon materials.

The polyanthracene described herein can be used as carbon precursors forthe preparation of carbon fibers and carbon fiber-reinforced carboncomposite materials. In an illustrative embodiment, carbon fiber is madeusing the polyanthracene described herein. In brief, the polyanthracenecan be drawn into long strands of fibers and then heated to a very hightemperature in the absence of oxygen until the fibers are carbonized;the produced carbon fibers can be used to make products such as racingcar bodies, golf club shafts, bicycle frames, fishing rods, automobilesprings, sailboat masts, and many other products where light weight andhigh strength are desirable. The polyanthracene described herein mayalso be used to make nanotubes that can make high-strength fibers,submicroscopic test tubes, and new semiconductor materials forintegrated circuits (for review, please see: P. Morgan, Carbon fibersand their composites, published by CRC Press (2005); B. George et al,Materials Handbook, Published by McGraw-Hill, 1997; Ebbesen, T. W.“Carbon Nanotubes.” Physics Today, 26-32 (1996 June)). In anotherillustrative embodiment, carbon fiber-reinforced carbon compositematerials are made using the polyanthracene described herein (forreviews on production method, please see: P. Morgan, Carbon fibers andtheir composites, published by CRC Press (2005)). The obtained carbonfiber-reinforced carbon composite materials can be used in automotiveapplications and railway applications, such as components of the brakesystems on high performance road cars or on high-speed trains (e.g.brake disc and brake pads).

The polyanthracene described herein has moderate electrical conductivityand thus can be used to conduct electricity. In an illustrativeembodiment, the polyanthracene or the doped polyanthracene can be usedas an additive in materials that have no or poor electrical conductivityso as to improve the conductivity of the materials. In anotherillustrative embodiment, the polyanthracene can be used as an additivein materials that tend to accumulate static electricity so as to preventaccumulation of static electricity in such materials. In anotherillustrative embodiment, the polyanthracene may be used in a packagingmaterial to prevent accumulation of static electricity in the material.

The polyanthracene described herein can have wide applications. Forexample, they may be used to make an anti-ablation paint, rechargeablebattery, ultra-capacitor, and carrier for catalysts (D. Fauteux et al,“Lithium polymer electrolyte rechargeable battery,” Electrochimica Acta,40(13-14): 2185-2190 (1995); A. B. Strong, “Fundamentals of compositesmanufacturing: materials, methods and applications,” published by SME,Edition 2, p 133-136 (2007); M. Stasiak et al, “Polymer Fibers asCarriers for Homogeneous Catalysts,” Chemistry—A European Journal,13(21): p 6150-6156(2007).). In another aspect, the present disclosureprovides anti-ablation paint including the polyanthracene of the presentdisclosure. In another aspect, the present disclosure providesrechargeable battery including the polyanthracene of the presentdisclosure. In another aspect, the present disclosure providesultra-capacitor including the polyanthracene of the present disclosure.In another aspect, the present disclosure provides and carrier forcatalysts including the polyanthracene of the present disclosure.

In another aspect, the present disclosure provides polyanthracene usefulfor making thermal resistant materials or ablation resistant materials.In another aspect, the present disclosure provides thermal resistantmaterials including the polyanthracene of the present disclosure. Inanother aspect, the present disclosure provides ablation resistantmaterials including the polyanthracene of the present disclosure.

In another aspect, the present disclosure provides polyanthracene usefulfor making carbon precursors for the preparation of carbon fibers andcarbon fiber-reinforced carbon composite materials. In another aspect,the present disclosure provides carbon precursors for the preparation ofcarbon fibers and carbon fiber-reinforced carbon composite including thepolyanthracene of the present disclosure.

In another aspect, the present disclosure provides polyanthracene usefulfor making electrically conductive materials. In another aspect, thepresent disclosure provides an electrically conductive materialincluding the polyanthracene of the present disclosure.

In another aspect, the present disclosure provides polyanthracene usefulfor making anti-static electricity materials. In another aspect, thepresent disclosure provides an anti-static electricity materialincluding the polyanthracene of the present disclosure.

EXAMPLES

The following Examples are set forth to aid in the understanding of thepresent disclosure, and should not be construed to limit in any way thescope of the invention as defined in the claims which follow thereafter.

Example 1 Preparation of Polyanthracene in the Presence of FeCl₃,Nitromethane and Water

800 mg (4.488 mmol) anthracene is dissolved in 30 ml nitromethane. Thesolution is warmed up to the temperature of 80° C. 2184 mg (13.464 mmol)FeCl₃ is dissolved in 30 ml nitromethane and filtered. 0.48 ml water isadded to the filtered FeCl₃ solution and warmed up to 80° C. The FeCl₃solution is added into the anthracene solution. The mixture is incubatedin a water bath at 80° C. for 6 hours with a magnetic bar stirring. Thereaction is terminated with the addition of 60 ml 95% ethanol.

The reaction mixture is centrifuged to obtain the sediment. The sedimentis washed with water for 2-4 times until no Fe³⁺, Fe²⁺ or Cl⁻ ion aredetected in the wash out. Then the sediment is washed with ethanol for3-5 times until the wash out show no coloring or only light coloring. Tofurther remove Fe³⁺ or Fe²⁺ contaminants, the resulting polyanthraceneis added into 20 ml 1M HCl and the mixture is stirred for a whole day.The mixture is centrifuged to collect the sediment. The sediment iswashed with water until the wash out has neutral pH value. Then theresulting polyanthracene is added into 30 ml 0.2M NH₃ and the mixture isstirred for a whole day. Then the mixture is centrifuged to obtain thesediment, which is in turn washed with water until the wash out becomesneutral. The washed sediment is dried at 80° C. until the residualproduct reaches constant weight. The resulting polyanthracene is a darkbrown powder. The production yield is 38.1%.

The polyanthracene is soluble in organic solvents such as NMP(solubility: 27.1 g/l), DMF (solubility: 25.3 g/l), DMSO (solubility:24.1 g/l), THF (solubility: 26.6 g/l), and CHCl3 (solubility: 24.9 g/l).Its UV-visible spectrum shows strong absorption at the wavelength ofabout 685 nm. Its electrical conductivity in its virgin salt state is7.0×10⁻⁹ S cm⁻¹, and the electrical conductivity after iodine doping is7.5×10⁻⁴ S cm⁻¹. According to the MALDI-TOF-MS method, thepolymerization degree is about 18 units of anthracene monomers, and themolecular weight is about 3200 (FIG. 2). The polyanthracene remainstable after being heated to 350° C. in air. When the polyanthracene isheated from room temperature to 1,000° C. at the rate of 20° C./min inthe presence of nitrogen, the thermal decomposition temperature at whichthe polyanthracene reaches maximum decomposition rate is identified as530° C., and the residual product is a dark char with metallic luster.The char yield is 81.5% and the electrical conductivity of the char is51.5 S cm⁻¹.

Example 2 Preparation of Polyanthracene in the Presence of FeCl₃,Dichloromethane/Nitromethane and Water

800 mg (4.488 mmol) anthracene is dissolved in 30 ml dichloromethane.The solution is warmed up to the temperature of 30° C. 6552 mg (40.392mmol) FeCl₃ is dissolved in 30 ml nitromethane and filtered. 0.72 ml(40.392 mmol) water is added to the filtered FeCl₃ solution and warmedup to 30° C. The FeCl₃ solution is added into the anthracene solution.The mixture is incubated in a water bath at 30° C. for 6 hours with amagnetic bar stirring. The reaction is terminated with the addition of60 ml 95% ethanol.

The reaction mixture is centrifuged to obtain the sediment. The sedimentis washed with water for 2-4 times until no Fe³⁺, Fe²⁺ or Cl⁻ ion aredetected in the wash out. Then the sediment is washed with ethanol for3-5 times until the wash out show no coloring or only light coloring. Tofurther remove Fe³⁺ or Fe²⁺ contaminants, the resulting polyanthraceneis added into 20 ml 1M HCl and the mixture is stirred for a whole day.The mixture is centrifuged to collect the sediment. The sediment iswashed with water until the wash out becomes neutral. Then the resultingpolyanthracene is added into 30 ml 0.2M NH₃ and the mixture is stirredfor a whole day. Then the mixture is centrifuged to obtain the sediment,which is in turn washed with deionized water until the wash out becomesneutral. The washed sediment is dried at 80° C. until the residualproduct reaches constant weight. The residual product is a dark brownpowder. The production yield is 25.0%.

The polyanthracene is soluble in organic solvents such as NMP(solubility: 25.0 g/l), DMF (solubility: 20.6 g/l), DMSO (solubility:19.8 g/l), THF (solubility: 23.4 g/l), and CHCl₃ (solubility: 23.1 g/l).Its UV-visible spectrum shows stronger absorption at the wavelength ofabout 380 nm, 470 nm, 480 nm, 610 nm, and 690 nm (FIG. 3). Theelectrical conductivity of the polyanthracene in its virgin salt stateis less than 10⁻¹¹ S cm⁻¹, and increases to 4.0×10⁻⁴ S cm⁻¹ after dopingby iodine.

Example 3 Preparation of Polyanthracene in the Presence of FeCl₃,Dichloromethane/Nitromethane at the Reaction Temperature of 20° C.

800 mg (4.488 mmol) anthracene is dissolved in 30 ml dichloromethane.The solution is warmed up to the temperature of 20° C. 6552 mg (40.392mmol) FeCl₃ is dissolved in 30 ml nitromethane and filtered. Thefiltered FeCl₃ solution is warmed up to 20° C. in a water bath. TheFeCl₃ solution is added into the anthracene solution with a magnetic barstirring. The mixture is incubated in a water bath at 20° C. for 6 hourswith a magnetic bar stirring. The reaction is terminated with theaddition of 60 ml ethanol.

The reaction mixture is centrifuged to obtain the sediment. The sedimentis washed with ethanol to remove any remaining monomer and oligomer.Then the sediment is washed with deionized water for 2-4 times until noFe³⁺, Fe²⁺ or Cl⁻¹ ion is detectable in the wash out with 0.1M NaOH. Tofurther remove any remaining anthracene monomers and low molecularweight polymers, the sediment is washed with ethanol for 3-5 times untilthe wash out show no coloring or only light coloring. The washedsediment is dried at 80° C. until it reaches constant weight. Theresulting polyanthracene is a dark brown powder. The production yield is66.3%.

The polyanthracene is partially soluble in organic solvents such as NMP(solubility: 17.7 g/l), DMF (solubility: 16.9 g/l), DMSO (solubility:16.3 g/l), THF (solubility: 17.2 g/l), and CHCl₃ (solubility: 15.4 g/l).Its UV-visible spectrum shows stronger absorption at the wavelength ofabout 380 nm, 460 nm, and 480 nm (FIG. 4). Its electrical conductivityin virgin salt state is about 1.0×10⁻⁹ S cm⁻¹, and increases to 2.3×10⁻³S cm⁻¹ after doping by iodine. According to the MALDI-TOF-MSmeasurement, the polymerization degree is about 10, and the molecularweight is about 1722. The polyanthracene remains stable in air at atemperature below 300° C.

Example 4 Preparation of Polyanthracene in the Presence of FeCl₃,Dichloromethane/Nitromethane at the Reaction Temperature of 30° C.

800 mg (4.488 mmol) anthracene is dissolved in 30 ml dichloromethane.The solution is warmed up to the temperature of 30° C. 6552 mg (40.392mmol) FeCl₃ is dissolved in 30 ml nitromethane and filtered. Thefiltered FeCl₃ solution is warmed up to 30° C. in a water bath. TheFeCl₃ solution is added into the anthracene solution with a magnetic barstirring. The mixture is incubated in a water bath at 30° C. for 6 hourswith a magnetic bar stirring. The reaction is terminated with theaddition of 60 ml ethanol.

The produced polyanthracene is washed and isolated as described inExample 3. The resulting polyanthracene is a dark brown powder. Theproduction yield is 78.3%.

The polyanthracene is partially soluble in organic solvents such as NMP(solubility: 14.1 g/l), DMF (solubility: 13.4 g/l), DMSO (solubility:10.8 g/l), THF (solubility: 11.9 g/l), and CHCl₃ (solubility: 9.7 g/l).Its UV-visible light excitation result shows stronger absorption at thewavelength of about 380 nm, 460 nm, and 480 nm (FIG. 4). Its electricalconductivity in virgin salt state is about 5.4×10⁻⁹ S cm⁻¹, andincreases to 1.1×10⁻² S cm⁻¹ after doping by iodine. According to theMALDI-TOF-MS measurement, the polymerization degree is about 7, and themolecular weight is about 1230. The polyanthracene remains stable in airat a temperature below 300° C. When the polyanthracene is heated fromroom temperature to 1,000° C. at the rate of 20° C./min in the presenceof nitrogen, the thermal decomposition temperature is identified as 466°C. (FIG. 5( a)), and the residual product is a dark bulk-like solidsubstance. The char yield is 71.1% (FIG. 5( a)) and the electricalconductivity of the char is 5.8 S cm⁻¹.

Example 5 Preparation of Polyanthracene in the Presence of FeCl₃,Dichloromethane/Nitromethane at the Reaction Temperature of 40° C.

800 mg (4.488 mmol) anthracene is dissolved in 30 ml dichloromethane.The solution is warmed up to the temperature of 40° C. 6552 mg (40.392mmol) FeCl₃ is dissolved in 30 ml nitromethane and filtered. Thefiltered FeCl₃ solution is warmed up to 40° C. in a water bath. TheFeCl₃ solution is added into the anthracene solution with a magnetic barstirring. The mixture is incubated in a water bath at 40° C. for 6 hourswith a magnetic bar stirring. The reaction is terminated with theaddition of 60 ml ethanol.

The produced polyanthracene is washed and isolated as described inExample 3. The resulting polyanthracene is a brownish black powder. Theproduction yield is 81.8%.

The polyanthracene is partially soluble in organic solvents such as NMP(solubility: 13.8 g/l), DMF (solubility: 13.1 g/l), DMSO (solubility:10.6 g/l), THF (solubility: 11.7 g/l), and CHCl3 (solubility: 9.4 g/l).Its UV-visible light excitation result shows stronger absorption at thewavelength of about 380 nm, 460 nm, and 480 nm (FIG. 4). Its electricalconductivity in virgin salt state is about 4.1×10⁻¹¹ S cm⁻¹, andincreases to 6.8×10⁻³ S cm⁻¹ after doping by iodine. According to theMALDI-TOF-MS measurement, the polymerization degree is about 6, and themolecular weight is about 1050. The polyanthracene remains stable in airat a temperature below 300° C.

Example 6 Preparation of Polyanthracene in the Presence of FeCl₃,Dichloromethane/Nitromethane at the Reaction Temperature of 80° C.

800 mg (4.488 mmol) anthracene is dissolved in 30 ml dichloromethane atroom temperature. 6552 mg (40.392 mmol) FeCl₃ is dissolved in 30 mlnitromethane and filtered. The filtered FeCl₃ solution is warmed up to80° C. in a water bath. Then the FeCl₃ solution is added in one portionto the anthracene solution, and the mixture is then incubated in thewater bath at 80° C. for 6 h with a magnetic bar stirring. The condensertube is needed to avoid the evaporation of dichloromethane solvent inthis circumstance. The reaction is terminated with the addition of 60 mlethanol.

The produced polyanthracene is washed and isolated as described inExample 3. The resulting polyanthracene is a brownish black powder. Theproduction yield is 94.0%.

The polyanthracene is partially soluble in organic solvents such as NMP(solubility: 12.5 g/l), DMF (solubility: 12.0 g/l), DMSO (solubility:9.9 g/l), THF (solubility: 10.8 g/l), and CHCl3 (solubility: 9.0 g/l).Its UV-visible light excitation result shows stronger absorption at thewavelength of about 380 nm, 460 nm, and 480 nm (FIG. 4). Its electricalconductivity in virgin salt state is about 2.2×10⁻⁹ S cm⁻¹, andincreases to 3.6×10⁻⁴ S cm⁻¹ after doping by iodine. According to theMALDI-TOF-MS measurement, the polymerization degree is about 8, and themolecular weight is about 1400. The polyanthracene remains stable in airat a temperature below 300° C. When the polyanthracene is heated fromroom temperature to 1,000° C. at the rate of 20° C./min in the presenceof nitrogen, the thermal decomposition temperature is identified as 736°C. (FIG. 5( b)), and the residual product is a dark bulk-like solidsubstance. The char yield is 70.4% (FIG. 5( b)) and the electricalconductivity of the char is 3.9 S cm⁻¹.

100 mg of the polyanthracene produced by the method described in thisexample is extracted twice with 5 ml THF for 60 min, and the insolublepart is collected by centrifugation and dried at 80° C. in air for 24 hwith the yield of about 50%. The obtained polyanthracene is relativelyconcentrated with polyanthracene molecules of high molecular weight andrigid chain structure compared with those dissolved in THE When thepolyanthracene is heated from room temperature to 1,000° C. at the rateof 10° C./min in the presence of nitrogen, the thermal decompositiontemperature is identified as 740° C. (FIG. 5( c)), and the residualproduct is a dark solid substance with metal luster. The char yield is70.0% (FIG. 5( c)) and the electrical conductivity of the char is 1166.7S cm⁻¹.

General

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application.

It will be understood by those within the art that, in general, termsused herein, and especially in the appended claims (e.g., bodies of theappended claims) are generally intended as “open” terms (e.g., the term“including” should be interpreted as “including but not limited to,” theterm “having” should be interpreted as “having at least,” the term“includes” should be interpreted as “includes but is not limited to,”etc.). It will be further understood by those within the art that if aspecific number of an introduced claim recitation is intended, such anintent will be explicitly recited in the claim, and in the absence ofsuch recitation no such intent is present. For example, as an aid tounderstanding, the following appended claims may contain usage of theintroductory phrases “at least one” and “one or more” to introduce claimrecitations. However, the use of such phrases should not be construed toimply that the introduction of a claim recitation by the indefinitearticles “a” or “an” limits any particular claim containing suchintroduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (e.g., “a” and/or “an” should be interpreted to mean “at least one”or “one or more”); the same holds true for the use of definite articlesused to introduce claim recitations. In addition, even if a specificnumber of an introduced claim recitation is explicitly recited, thoseskilled in the art will recognize that such recitation should beinterpreted to mean at least the recited number (e.g., the barerecitation of “two recitations,” without other modifiers, means at leasttwo recitations, or two or more recitations).

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, such as in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” “greater than,” “less than,” and the likeinclude the number recited and refer to ranges which can be subsequentlybroken down into subranges as discussed above. Finally, as will beunderstood by one skilled in the art, a range includes each individualmember. Thus, for example, a group having 1-3 members refers to groupshaving 1, 2, or 3 members and so forth.

The present disclosure is not to be limited in terms of the particularembodiments described in this application, which are intended asillustrations of various aspects. Many modifications and variations canbe made without departing from its spirit and scope, as will be apparentto those skilled in the art. Functionally equivalent methods andproducts within the scope of the disclosure, in addition to thoseenumerated herein, will be apparent to those skilled in the art from theforegoing descriptions. Such modifications and variations are intendedto fall within the scope of the appended claims. The present disclosureis to be limited only by the terms of the appended claims, along withthe full scope of equivalents to which such claims are entitled. It isto be understood that this disclosure is not limited to particularmethods, reagents, compounds compositions or biological systems, whichcan, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular embodimentsonly, and is not intended to be limiting.

While various aspects and embodiments have been disclosed herein, otheraspects and embodiments will be apparent to those skilled in the art.The various aspects and embodiments disclosed herein are for purposes ofillustration and are not intended to be limiting, with the true scopeand spirit being indicated by the following claims.

We claim:
 1. A method of producing polyanthracene, comprising: forming apolymerization reaction mixture comprising anthracene monomers, at leastone oxidant and at least one reaction solvent, wherein the anthracenemonomers are represented by formula I

maintaining the polymerization reaction mixture under conditionseffective to covalently bond two or more anthracene monomers to form oneor more polyanthracenes, wherein the weight average molecular weight ofthe one or more polyanthracenes is no less than 3000 and 5% to 80% ofthe one or more polyanthracenes by weight contains 18 or more units ofanthracene monomers represented by formula I.
 2. The method of claim 1,wherein the oxidant is a Lewis acid.
 3. The method of claim 1, whereinthe oxidant is selected from the group consisting of FeCl₃, FeBr₃,AlCl₃, AlBr₃, AlI₃, AlRCl₂, AlR₂Cl, AlR₃, CuCl₂, CuBr₂, MoCl₅, SnCl₄,SnBr₄, SnI₄, MgCl₂, MgBr₂, MgI₂, CaCl₂, CaBr₂, CaI₂, ZnCl₂, ZnBr₂, ZnI₂,BF₃, TiCl₄, TiBr₄, SbCl₅, and any combination thereof.
 4. The method ofclaim 3, wherein the oxidant is FeCl₃.
 5. The method of claim 1, whereinthe molar ratio of the oxidant to the anthracene monomers ranges from1:1 to 9:1.
 6. The method of claim 1, wherein the reaction solvent isselected from the group consisting of nitroalkanes, aromatic nitrocompounds, hydrocarbons, halogenated hydrocarbons, nitriles, and anycombination thereof.
 7. The method of claim 1, wherein the reactionsolvent is selected from the group consisting of nitromethane,nitroethane, nitrobenzene, dinitrobenzene, hexane, benzene, pentane,isooctane, cyclohexane, dichloromethane, chloroform, dichloroethane,dichlorobenzene, bromoethane, dibromoethane, bromobenzene,dibromobenzene, bromopentane, carbon tetrachloride, acetonitrile,propionitrile butyronitrile, and any combination thereof.
 8. The methodof claim 1, wherein the maintaining step is performed at a temperatureranging from 20 to 100° C.
 9. The method of claim 8, wherein thetemperature ranges from 20 to 80° C.
 10. The method of claim 9, whereinthe temperature ranges from 20 to 40° C.
 11. The method of claim 1,wherein the polymerization reaction mixture contains water.
 12. Themethod of claim 1, wherein the maintaining step is performed for 1 to 24hours.
 13. A composition comprising one or more polyanthracenes, whereinthe one or more polyanthracenes are produced by a method comprising:polymerizing anthracene monomers in the presence of an oxidant and areaction solvent, wherein 5% to 80% of the one or more polyanthracenesby weight contains 18 or more units of anthracene monomers.
 14. Thecomposition of claim 13, wherein the thermal decomposition temperatureof the one or more polyanthracenes is 400 ° C. or higher in the presenceof nitrogen.
 15. The composition of claim 13, wherein the electricalconductivity of the one or more polyanthracenes in nascent state is from10 ⁻⁹ to 10 ⁻¹¹ S cm⁻¹.
 16. The composition of claim 13, wherein thechar yield of the one or more polyanthracenes at 1000 ° C. is from 70%to 95%.
 17. The composition of claim 13, wherein 5% to 100% of the oneor more polyanthracenes by weight is soluble in an organic solvent. 18.The composition of claim 17, wherein the organic solvent is selectedfrom the group consisting of N-methylpyrrolidone (NMP), tetrahydrofuran(THF), chloroform, dimethylformamide (DMF), and dimethylsulfoxide(DMSO).
 19. The composition of claim 13, wherein the one or morepolyanthracenes have absorbance peaks at wavelengths ranging from 380 nmto 690 nm.
 20. The composition of claim 13, wherein the composition isselected from the group consisting of a thermal resistant material, anablation resistant material, a carbon precursor, an electricallyconductive material, an anti-static electricity material, ananti-ablation paint, a rechargeable battery, an ultra-capacitor, and acarrier for catalysts.